POLYMER CHEMISTRY

UNIT I

POLYMER CHEMISTRY

Polymers are macromolecules (giant molecules of high molecular masses)

built up by the linking together of a large number of small molecules (monomers). In
greek, ‘poly’ refers to many and ‘mers’ refers to units or parts.

For ex. polythene is a polymer formed by linking together of a large number of

ethene (C 2H4) molecule. Thus,

Thus small molecules which combine with each other to form polymer
molecules are termed ‘monomers’ and the repeat unit in a polymer is called ‘mer’.

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MONOMERS

NOMENCLATURE OF POLYMERS

(a) A polymer may consist of identical monomers (M) or monomers of different

chemical structure (M1, M2 etc). Accordingly they are called homopolymers
and copolymers respectively.

-M-M-M-M-M- -M1-M2 -M1-M2 -M1-M2-

Homopolymer Copolymer

The monomeric unit in a polymer may be present in linear, branched or

crosslinked (3 dimensional structure)

(i) –M-M-M-M-M- -M1-M2 -M1-M2 -M1-M2-

Linear homopolymer Linear copolymer

M1
M2
(ii) –M-M-M-M-M- –M1-M2-M1-M2-M1 -
M M1
M M2
M M1

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(Branching of same monomer) (Branching of comonomers)

(iii) –M-M-M-M-M-M-M-M-
M M
-M- M-M-M-M-M-M-M-
M M
M M
-M- M-M-M-M-M-M-M-
(Cross linked homopolymer)

If the main chain is made up of same species of atoms, the polymer is called
homochain polymer.

-C-C-C-C-C- (Homochain)

-C-C-O-C-C-O-C- (Heterochain)

Graft Copolymers:

They are branched structures in which the monomer segments on the branches and
the backbone differ.

-M1-M1 -M1-M1 -M1-

M2 M2

M2 M2
M2 M2

CLASSIFICATION OF POLYMERS:

On the basis of source, polymers are classified as

(i) Natural polymers

(ii) Synthetic polymers

i) Natural polymers: They are found in nature in animals and plants. Ex.
Starch (a polymer of  -D-glucose), Cellulose (a polymer of  - D-glucose),

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proteins (polypeptides and polyamides), Nucleic acids, Natural rubber (a

polymer of cis-isoprene).

ii) Synthetic polymers: (man made polymers): ex. Polyethylene

(PE).Polypropylene (PP), Polystyrene (PS), Polyvinyl chloride (PVC),
Nylon, terylene, bakelite etc.

CLASSIFICATION OF POLYMERS BASED ON MOLECULAR FORCES:

On the basis of the magnitude of intermolecular forces present in

polymers, they are classified into four categories.

i) Thermoplastic Polymers: These are linear, long chain polymers which can
be softened on heating and harden on cooling reversibly (i.e.) their
hardness is a temporary property, subject to cha nge with rise or fall of
temperature. Thus they can be processed again and again. (ex) Polythene
(PE), Polypropylene (PP), Polyvinyl chloride (PVC), Polystyrene (PS),
nylon, Polytetrafluoro ethylene (PTFE or Teflon etc).

ii) Thermosetting Polymers (or thermosets): These are polymers which

during molding (by heating etc) get hardened and once they have solidified
they cannot be softened. (i.e.) they are permanent setting polymers. Such
polymers during moulding acquire three dimensional cross linked
structures with predominantly strong covalent bonds. Thus a thermosetting
polymer once molded cannot be reprocessed. (ex) Polyester (terylene),
bakelite, epoxy-resin (araldite), melamine, urea-formaldehyde etc.

iii) Elastomer (or synthetic rubber): It is a rubber like elastic polymer which
can be stretched to at least thrice its length, but returns to its original
shape and dimensions as soon as stretching force is released. The elastic
deformation in an elastomer arises from the fact that in an unstressed
condition, an elastomer molecular chain is in the form of a coil and
consequently it can be stretched like a spring. The chain reverts back to
their original coiled state as the deforming stress is released. Thus

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elasticity of an elastomer is caused by the lengthening and shortening of

their polymeric chain springs.

iv) Fibres: These are polymers whose chains are held by strong
intermolecular forces like hydrogen bonding. They are crystalline in nature
and of high tensile strength due to strong intermolecular forces. (ex) Nylon,
Polyester etc

Hydrogen bonding in Nylon 6,6

Thermoplastic versus thermosetting polymers

S.No. THERMOPLASTIC POLYMERS THERMOSETTING POLYMERS

1 They consist of long chain linear They consist of three dimensional
macromolecules network structure joined by strong
covalent bonds
2 They are formed mostly by They are formed by condensation
addition polymerisation polymerisation
3 By reheating to a suitable They retain their shape and structure
temperature, they can be softened, even on heating. Hence they cannot be
reshaped and thus reused reshaped and reused
4 They are usually soft, weak and They are usually hard, strong and more
less brittle brittle
5 They can be reclaimed from They cannot be reclaimed from wastes
wastes
6 They are usually soluble in organic Due to strong crosslinking, they are
solvents insoluble in almost all organic solvents

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(ex) Polyethylene, polypropylene (ex) Bakelite, Epoxy resin etc

etc

CLASSIFICATION OF POLYMERS BASED ON STRUCTURE:

Based on the structure, the polymers are classified as

(i) Linear Polymers

(ii) Branched Polymers

(iii) Cross-linked Polymers

(i) Linear Polymers: The bifunctional monomeric units are linked together to form a
long linear straight chain. (ex), bifunctional ethylene monomer polymerises to yield
linear structure of high density polyethylene (HDPE). All the thermoplastic polymers
are essentially linear molecules.

(ii) Branched chain Polymers: Branched chain polymer is formed when a

bifunctional monomer is mixed and polymerised with a little amount of trifunctional
monomer. Branched polymers contain molecules having a linear backbone with
branches arising randomly from it. For example, low-density PE (LDPE), polystyrene
etc.

(iii) Cross linked polymers: When the functionality of the monomer is 3 and above,
cross-linked three-dimensional network of polymer is formed. In fact, whenever a
multifunctional monomer is polymerised, the polymer ultimately forms a network
polymer. For example, Bakelite, urea-formaldehyde etc.

CLASSIFICATION OF POLYMERS BASED ON SYNTHESIS

(i) Addition (Chain-Growth) Polymerization

(ii) Condensation (Step-Growth) Polymerization

(iii) Copolymerisation

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(i) Addition Polymerisation:

A polymerisation reaction in which monomers containing one or more double bonds

are linked to each other without the elimination of any byproducts, usually in the
presence of free radical initiator is called addition polymerisation. Since in this
polymerisation the monomers are linked by a chain reaction, it is also chain
polymerisation and the polymers formed are called chain-growth polymers. For
example, the formation of PE.

The main features of addition polymerisation are:

1. Only olefinic or vinyl compounds can undergo addition polymerization

2. No elimination of by-products.
3. Double bond provides required bonding sites.
4. The addition of monomers takes place rapidly.
5. Polymerization is brought about by initiators like free radicals.
6. The elemental composition of the polymer is the same as that of the
monomer.

(ii) Condensation Polymerisation: Polymerisation reactions in which bifunctional or

polyfunctional monomers undergo intermolecular condensation with continuous
elimination of by-products such as H2 O, HCl, NH3 etc is called condensation
polymerisation. Since the reaction occurs in steps and the polymer chain grows with
each step, it is also called step polymerisation and the polymers formed are called
step-growth polymers. The reaction is normally catalysed by acids or bases. Ex.
nylon 6,6, polyester etc.

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1.
Nylon 6,6

2.

The main features of condensation polymerisation are as follows

1. The monomers having two or more reactive functional groups can undergo
condensation polymerisation.
2. There is continuous elimination of byproducts.
3. Polymerisation proceeds through intermolecular condensation.
4. Polymerisation is catalysed by acids or alkali.
5. The polymer chain built up is slow and stepwise.
6. The elemental composition of the polymer is different from that of the
monomers.

(iii) Copolymerisation: The polymerisation of two or more different monomers

resulting in the formation of a polymer containing both monomers linked in one chain
is called copolymerisation. It can be considered as a type of addition polymerisation.
The polymers so formed are called copolymers and can have any of the three
following structures.

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If the various repeating units occur randomly along the chain structure,
the polymer is called a random copolymer. When repeating units of each kind appear
in blocks, it is called a block copolymer. Graft copolymers are formed when chains of
one kind are attached to the backbone of a different polymer.

FUNCTIONALITY

The number of bonding sites in a monomer is referred to as its functionality.

For a substance to act as a monomer, it must have atleast two reactive sites or
bonding sites. In an olefin, the double bond can be considered as a site for two free
valancies. When the double bond is broken, two single bonds become available for
combination.

H H H H

C=C -------C-C------

H H H H

Thus ethylene is considered to be bifunctional.

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i) Depending upon the functionality of the monomeric units, it is possible to

obtain different types of structures. In case of a bifunctional monomer, two
reactive groups attach side by side to each other forming a linear or
straight chain molecule. Linear molecules consist of monomer units linked
by primary covalent bonds, but different chains are held together by
secondary vanderwaals forces of molecular attraction. This gives the
possibility of chain movement in one direction.

These polymers are soft and flexible, have less strength, low heat
resistance and are soluble in organic solvents.

ii) During the chain growth, side chains may also form resulting in branched
chain molecules. In such a molecule, the movement is restricted than that
of simple straight chain molecules. A branched chain polymer results when
a trifunctional monomer is mixed in small amounts with a bifunctional
monomer and polymerized.

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iii) In polyfunctional groups, the monomer molecules are connected by

covalent bonds and forms three dimensional network of molecules. The
movement of individual molecules are prevented by strong crosslinks.

These polymers are hard and brittle and have greater strength and heat
resistance. It is insoluble in almost all organic solvents.

DEGREE OF POLYMERISATION

The number of repeating units (n) in the polymer chain is known as degree of
polymerization.

M.wt of polymeric network

Degree of polymerization =

M.wt of repeating unit

TYPES AND MECHANISM OF POLYMERISATION

I. Addition or chain growth polymerisation

II. Condensation or stepwise polymerisation
III. Copolymerisation

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I. Addition or Chain growth polymerisation:

It is a reaction that yields a polymer, which is an exact multiple of the
original monomeric molecule. There is no elimination of any molecule.

MECHANISM OF ADDITION POLYMERISATION

It can be carried out by any of the following mechanism.

1. Free radical polymerisation

2. Cationic mechanism
3. Anionic mechanism

1. FREE RADICAL POLYMERISATION:

The initiation of the polymer chain growth is brought about by free radicals
produced by the decomposition of compounds called initiators. The term
‘chain growth’ represents a process involving a continuous and very rapid
addition of the monomer units to form polymer molecules or polymer chains.
As more and more monomer units are added, the length of the polymer
chains increases continuously and the chains grow rapidly.
(i) Initiation Step:
Initiators are thermally unstable compounds and decompose into products
called free radicals.

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It involves two reactions.

(a) First, is the production of free radicals by homolytic dissociation (each

component carries with it one of the electrons from the electron pair) of an
initiator to yield a pair of radicals R. The decomposition of the initiator to
form free radicals can be induced by heat energy, light energy, uv light or
catalysts. Examples of initiator include benzoyl peroxide, azobis isobutyro
nitrile etc.

I 2R
(Initiator) (free radicals )

(b) Second part of initiation involves the addition of this radical to the first
monomer molecule to produce chain initiating species. A free radical is highly
reactive and can attack any molecule which either has a lone electron or is
prepared to part with one of its electrons. This is what happens in the process
of initiation. The free radical R attacks the double bond in the monomer
molecule resulting in the following chemical change.

(ii) Propagation:

After initiation comes propagation. In the propagation step, the radical site at the first
monomer unit attacks the double bond of a fresh monomer molecule. This results in
the linking up of the second monomer unit to the first and the transfer of the radical
site from the first monomer unit to the second by the unpaired electron transfer
process.

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This process involving a continuing attack on fresh monomer molec ules (n) which in
turn keep successively adding to the growing chain one after another is termed
‘propagation’. It would continue until the supply of monomer was exhausted.

(iii) Termination:

After propagation comes termination. In this step, further addition of the monomer
units to the growing chain is here-after stopped and the growth of the polymer chain
is arrested. Depending on factors such as temperature, time, monomer and initiator
concentration there exists a statistical probability of the two growing chains coming
close to and colliding with each other. Termination can take place in two ways.

1) Combination or coupling:
In this case the two growing chains unite by the coupling of the lone electron
present in each chain to form an electron pair and thus nullify their
reactiveness. Since this process involves the coupling of the two lone electrons,
this kind of termination is known as termination by coupling.

+ 

2) Disproportionation:
In this case, one H from one growing chain is abstracted by the other growing
chain and utilized by the lone electron for getting stabilied, while the chain
which had donated the H gets stabilised by the formation of a double bond. In
this case, the termination process results in the formation of two polymer
molecules of shorter chain length as against a single molecule of a longer chain
length as obtained by the combination method. This type of termination is
called termination by disproportionation. The polymer molecule formed can be
referred to as a ‘dead’ polymer chain. The term dead polymer signifies the
cessation of growth of propagating radical.

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+ 

2. IONIC POLYMERISATION:
The ionic mechanism of chain polymerisation also involves an attack of the 
electron pair of the monomer. This time, however, not by the unpaired electron of the
free-radical but by either a positive or a negative ion.

(i) CATIONIC POLYMERISATION:

(i) Initiation:

It involves a system where a proton is introduced into a monomer. The proton pulls
the  electron pair towards it and the positive charge is transferred to the farther end
of the monomer molecule forming a carbonium ion. In this process a sigma bond is
formed between the proton and the monomer unit and the polymer chain growth is
‘initiated’. This is represented as follows:

(Carbonium ion)
The carbonium ion (C +) attacks the  electron pair of the second monomer molecule
and pulls it over; the positive charge is transferred to the farther end of the second
monomer unit.

+ 

In this reaction, only a displacement of the electron pair as a whole and the formation
of a carbonium ion take place. Strong Lewis acids such as BF 3 (generally called the
catalysts in ionic polymerisation) in the presence of small amounts of water or
methanol (known as co-catalysts) form hydrates which exist as ion pairs.

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(OR) Simply

Where, H+ is the initiating cationic species and is the counter-ion. The H+

proton now attacks the  electron of the monomer, starts the chain growth through

the carbonium ion and the anion faces the growing chain end.
+ 

This step constitutes the initiation step of the polymerisation.

(ii) Propagation:

The propagation reaction involves further adding up of the monomer units and
simultaneous transfer of the charge to the newly added monomer unit.

+ 


+

As more and more monomer units are added up, the chain keeps on growing and in
doing so, the  electron pairs of the monomer units are pulled in a direction opposite
to the growth of the chain. Also, the C + ion keeps on moving in the direction of the
chain growth and the counter-ion, all the time, moves along with the C + ion.

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(iii) Termination:

Termination occurs when a collision between the growing C + ion and an anion (either
from the counter-ion of another growing chain or from some deliberately added
anion) takes place. The possible reactions that takes place during termination
involve the following two factors.

1. Donation of a proton to the counter-ion resulting in the formation of a double

bond at the end of the growing polymer molecule and the resultant arrest of
the chain growth.

This process of donation of a proton and the reformation of the BF3 hydrate is
called ion-pair precipitation
2. Formation of a covalent bond between the carbonium ion and the counter -ion
when the termination occurs by simple ‘coupling’


+ BF3

In both cases, however, regeneration of the initiator takes place. This type of
polymerisation, where the initiation is done by a proton and the propagation is
carried out by a carbonium ion is called ‘cationic polymerisation’. The initiators used
for this purpose in addition to BF3 include AlCl3, SnCl4 and TiCl4. Examples of
monomers that can undergo cationic polymerisation are isobutylene, styrene, methyl
styrene and many vinyl ethers.

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2. ANIONIC POLYMERISATION:

(i) Initiation:

In this type of polymerisation, an attack on the  electron pair of the monomer

is done by a negatively charged ion (i.e.) an anion. Such a system has extra
electrons and the resultant negative charge attacks the  electron pair, pushing it, as
far away as possible, that is, to the end of the molecule. At the same time, it forms a
sigma bond with the monomer molecule. The electron pair pushed to the end of the
molecule results in the formation of a carbanion.

(ii) Propagation: The carbanion thus formed now propagates the chain growth by
attacking the second monomer unit, pushing its  electron pair further away to the
end and forming a sigma bond with the new monomer unit.

The difference between the cationic and the anionic processes is that in the former
case, the movement of the electron pair is in a direction opposite to that of the chain
growth whereas in the latter case it is in the same direction as that of the chain
growth. The general type of initiators used in this case is the organoalkali
compounds (i.e. the alkyl and aryl derivatives of alkali metals) such as butyl lithium,
triphenyl methyl potassium and ethyl sodium. Alkali metal amides, alcoxides and
hydroxides can also be used for the anionic polymerisation process. Monomers
capable of undergoing anionic polymerisation include butadiene, isoprene, styrene
and acrylonitrile.

(iii) Termination: The termination in anionic polymerisation is however not usually a

spontaneous process and unless some impurities are present or some strongly ionic

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substances are added deliberately, invariably no termination occurs. Thus, if

polymerisation is carried out under controlled conditions and impurities are avoided,
the reaction proceeds till all the monomer is consumed. In this case, while there is no
more monomer left to be polymerised, the carbanions at the chain ends remain
potentially active. What this means is that if a fresh quantity of monomer is added the
polymerisation again goes on until all the freshly added monomer is consumed.
Again, the chain ends are active and studies have shown that polymerisation can be
restarted even after weeks by adding fresh monomer. It is as if the polymer is a
‘living entity’ and in fact the polymers produced by this technique are called ‘living
polymers’. They are alive and keep on growing as long as we supply a fresh
quantity of the monomer just as many of the living organisms grow as long as food is
available. The ‘living polymerisation technique’ is useful for many applications. Block
copolymers for example are prepared by employing this technique.

DIFFERENCES BETWEEN ADDITION AND CONDENSATION POLYMERISATION

No Addition Polymerisation Condensation Polymerisation

1 It is also called as chain growth It is also called as step growth or
polymerisation step wise polymerisation
2 The growth reaction adds repeating Any two molecular species present
units one at a time and takes place can react and takes place with
only with monomers having multiple monomers having reactive functional
bonds groups
3 Monomer concentration decreases Monomer disappears early in the
steadily throughout the reaction and reaction and there will be elimination
the polymerisation takes place without of simpler molecules like H2O, NH3 ,
elimination of simpler molecules HCl etc. At degree of polymerisation
10, less than 1 % monomer remain
4 High Polymer (Degree of Polymer mol.wt rises steadily and
polymerisation : 10,000 – 2,00,000) is does not require the presence of any
formed at once and requires the initiator
presence of initiator.
5 Long reaction time give high yields but Long reaction time are essential to
affect mol.wt slightly obtain high mol.wt

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PROPERTIES OF POLYMERS

GLASS TRANSITION TEMPERATURE:

The temperature below which a polymer is hard, brittle and above which
it is soft and flexible is called the glass transition temperature and it is denoted by T g.
The hard brittle state is called glassy state and soft flexible state is known as rubbery
state. In the glassy state, there is no segmental and molecular motion. On the other
hand, in rubbery state, there is only segmental motion but no molecular mobility. Tg
is an important property of polymer which decides if a polymer would behave like
glass or rubber. (ex) Tg of polystyrene is 1000C.

Factors affecting T g

1. Flexibility: Linear polymer chains made of C-C, C-O or C-N single bonds have a
higher degree of freedom of rotation on a single bond. Presence of rigid groups such
as aromatic and cyclic groups or bulky groups in the carbon chain backbone hinders
the freedom of rotation. This restriction in the chain mobility increases the T g value.
For example,

 In a linear polymer like PE, Tg is -110oC.

 In polyethylene terephthalate with cyclic group in the carbon chain backbone
Tg is 69oC.
 In polystyrene with aromatic group attached to one of the carbon atoms in the
carbon chain backbone, Tg is 100oC

2. Effect of side group: Poly (-methyl styrene) has higher Tg (170oC) while
polystyrene has lower Tg of 100oC due to the presence of extra methyl side group in
the former which hinders the free rotation about carbon-carbon bond of carbon chain
backbone. This restricts the chain mobility and thereby increases the Tg value.

3. Intermolecular Forces: Presence of a large number of polar groups in the

molecular chain lead to strong intermolecular cohesive forces, which restrict the
segmental/molecular mobility. This leads to an increase in Tg. For example,
polypropylene (Tg = -18oC) has lower Tg compared to nylon 6,6 (Tg = 57oC).

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4. Branching and cross-linking: A small amount of branching will reduce the value
of Tg , because the free volume increases with branching and thus decreases the Tg.
On the other hand, a high density of branching (crosslinking) brings the polymer
chains closer, lowers the free volume and thus reduces the chain mobility, thereby
increasing the value of Tg. For example, LDPE has lower value of Tg as compared to
cross-linking low density polyethylene (XLDPE).

5. Presence of plasticizers: Addition of plasticizers reduces the Tg value. For

example, diisooctyl phthalate (plasticizer), which when added to PVC reduces its T g
from 80oC to below room temperature.

6. Stereo-regularity: The Tg increases with the stereo-regularity of polymers. Thus,

Tg of a isotactic polymer is greater than that of a syndiotactic polymer, which in turn
has greater Tg than an atactic polymer.

7. Molecular weight: The Tg of all polymers, in general, increases with molecular

weight up to 20,000 and beyond this the effect is negligible.

SIGNIFICANCE OF Tg:

1. The Tg value is a measure of flexibility of a polymer and the type of response

the polymer would exhibit to mechanical stress.
2. Its value gives an idea of thermal expansion, heat capacity, refractive index,
electrical and mechanical properties of the polymer.
3. Its value can decide whether a polymer at the use temperature will behave
like a rubber or plastic.
4. Knowledge of Tg and Tm is useful in choosing the right temperature for
fabrication of materials. (Fabrication temperature is the region in which the
polymer material can be converted into a finished product through different
processing techniques, such as injection molding, compression molding,
calendaring, extrusion etc).

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TACTICITY:

The orientation of monomeric units in a polymer molecule can take place in an

orderly or disorderly fashion with respect to the main chain. The difference in
configuration (tacticity) do affect their physical properties.

(i) The head to tail configuration in which the functional groups are all on the
same side of the chain is called isotactic polymer. (ex) isotactic
polystyrene.

(ii) If the arrangement of functional gropus is at random around the main

chain, it is called atactic polymer. (ex) polypropylene.

(iii) If the arrangement of the functional groups is in alternating fashion, it is

called syndiotactic polymer. (ex) gutta percha

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MOLECULAR WEIGHT

During the process of polymerisation, polymer molecules with varying chain

length and varying extent of crosslinking between the different molecules are
produced. The concentration of monomer decides about the extent of crosslinking
and the chain length depends on the random encounter between the monomer and
the reactive site of the chain.
Due to randomness, all the polymer chains are not of same size and same
molecular weight. Hence the molecular weight of polymer (polydispersed material) is
expressed in terms of average value. In computing the molecular weight of a
polymer, we can use either the number fraction or the weight fraction of the
molecules present in the polymer to get either the number-average molecular weight
( ) or the weight-average molecular weight ( ) respectively.

Number-average molecular weight of the whole polymer will then be given by,

Similarly, total weight of the polymer = W =

Similarly, the weight – average molecular weight of the whole polymer will then be

For all synthetic polymers, is greater than If they were to be equal, the

polymer sample may be considered as perfectly homogeneous (i.e., each molecule

has the same molecular weight) but this does not happen.

(ii) POLYDISPERSITY INDEX: The weight – average molecular mass is always

greater than the number average molecular – mass. Moreover, since = in
case of monodisperse system (i.e, in which all molecules have identical molecular

mass), so the ratio may be used as a measure of the molecular – mass

distribution or an “index of polydispersity”.

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Since the contribution of different fractions on their average value of the

molecular weight depends on their weight proportions in case of and on their
number proportions in case of , so the high-molecular weight fractions will have a
greater effect on , and the low-molecular weight fractions will have a greater
effect on .

(Problems refer to Note Book)

TECHNIQUES OF POLYMERISATION:

The polymerisation on commercial scale is carried out principally by the

following methods:
(i) Bulk polymerisation
(ii) Solution polymerisation
(iii) Suspension polymerisation
(iv) Emulsion polymerisation

(1) BULK POLYMERISATION:

The monomer is taken in the liquid state and the initiator is dissolved in the
monomer. The chain transfer agent whenever used to control the molecular weight is
also dissolved in the monomer itself. The whole system is therefore in a
homogeneous phase. The reaction mass is heated or e xposed to a radiation source
for initiating the polymerisation and is kept under agitation for proper mass and heat
transfers. As the polymerisation proceeds, the viscosity of the medium increases and
mixing becomes progressively difficult leading to products with very broad molecular
weight distribution.
Another disadvantage of bulk polymerisation is that as the medium gets
viscous, the diffusibility of the growing polymer chains becomes restricted, the
probability of chain collision becomes less, termination becomes difficult, active
radical sites accumulate and the rate of polymerisation increases enormously. This
whole phenomenon is called ‘autoacceleration’ and sometimes the uncontrolled
exothermic reaction can lead to explosion.

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Bulk polymerisation however, is quite simple and the product obtained has a
high purity since, except the initiator and the chain transfer agent, no additive that
could contaminate the product is used. The polymer obtained can also be used as
such since no isolation from other components is involved.
Finally, the bulk polymerisation technique is used in the free radical
polymerisation of methyl methacrylate or styrene to get transparent moulding
powders and cast sheetings and also of vinyl chloride to get PVC resin.

(2) SOLUTION POLYMERISATION

In solution polymerisation, the monomer is dissolved in a suitable inert solvent
along with the chain transfer agent, whenever used. The free radical initiator is also
dissolved in the solvent medium, while the ionic and coordination catalysts, can
either be dissolved or suspended. The presence of the inert solvent medium helps to
control viscosity increase and promote a proper heat transfer.
The major disadvantage of the solution polymerisation technique is that,
however inert the selected solvent may be, chain transfer to the solvent cannot be
completely ruled out and hence it is difficult to get very high molecular weight
products. The polymer formed will also have to be isolated from the solution either by
evaporation of the solvent or by precipitation in a non-solvent and removal of their
fine traces is always extremely difficult. Solution polymerisation techniques
nevertheless can advantageously be used where the polymer is used in its solution
form as in the case of certain adhesives and coating compositions or in systems
where the polymer formed is insoluble in its monomer or solvent and precipitates out
as slurry and is amenable for easy isolation.
Industrial production of polyacrylonitrile by free radical polymerisation and that
of polyisobutylene by cationic polymerisation use the solution technique. Block co-
polymers are also made exclusively by this technique.

(3) SUSPENSION POLYMERISATION:

Only water-insoluble monomers can be polymerised by this technique. The
monomer is suspended in water, in the form of fine droplets, which are stabilised and
prevented from coalescing by using suitable water-soluble protective colloids,
surface active agents and by stirring. The size of the monomer droplets formed

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depends on the monomer-to-water ratio, the type and concentration of the stabilising
agent and also on the type and speed of agitation employed.
The initiators are monomer soluble. Since each monomer droplet is isolated
and independent of the other droplets, it can be visualised to act as an independent
bulk polymerisation nucleus. The continuous aqueous phase separating the
monomer droplets acts as an efficient heat transfer medium and hence the
exothermicity is well controlled. Since water is used as the heat transfer medium, the
process is also economical as compared to solution polymerisation. As the enture
bulk of the monomer is divided into innumerable tiny droplets, control on the kinetic
chain length of the polymer formed is also quite good, resulting in a fairly narrow
molecular weight distribution of the product. Polymerisation proceeds to 100 %
conversion and the product is obtained as spherical beads or pearls. For this reason,
this technique is also known as bead or pearl polymerisation. Isolation of the product
becomes easy as this involves only filtration of the beads and removal of the surface
active agents and protective colloids by water washing. The water -washed and dried
product can be used as such for moulding purposes or can be dissolved in a suitable
medium for use as adhesives and coatings.
Expandable polystyrene beads (from which polystyrene foams are made),
styrene- divinyl benene copolymer beads (for the preparation of ion-exchange
resins) and polyvinyl acetate beads (for further conversion into PVA) are produced
by the suspension technique using free-radical initiators.

(4) EMULSION POLYMERISATION:

As in the case of suspension polymerisation, in emulsion polymerisation too,

the monomer is dispersed in the aqueous phase not as discrete droplets but as a
uniform emulsion. The emulsion is stabilised by surface active agents (surfactants0,
protective colloids and also by certain buffers. The surfactants can be anionic 9alkali
salts of fatty acids and of aryl and alkyl sulfonic acids), cationic (alkyl amine
hydrochlorides and alkyl ammonium halides) or non-ionic (alkyl glycosides and
saccharose esters of fatty acids). Surfactants serve the purpose of lowering the
surface tension at the monomer-water interface and facilitate emulsification of the
monomer in water. Owing to their low solubility, surfactants get fully dissolved or
molecularly dispersed only at low concentrations. Beyond a particular concentration,
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 POLYMER CHEMISTRY

the excess quantity does not get molec ularly dispersed but forms molecular
aggregates known as ‘micelles’ and an equilibrium is set up between the dissolved
surfactant molecules and the aggregated ones. The highest concentration, wherein
all the molecules are in a dispersed state or the concentration beyond which only
micelle formation is possible, is known as the ‘critical micelle concentration (CMC).

In the micelle formation, the emulsifier molecules aggregate in such a way

that the polar ends of the molecules align themselves outward and the hydrocarbon
ends come close to each other at the interior. Due to the close proximity of the
hydrocarbon ends of all emulsifier molecules, the interior of the micelle acts as a
hydrocarbon phase where the monomer can be solubilised. Now, when the
monomer is added and agitated, emulsification takes place. The resultant emulsion
is a complex system: a molecular solution of the emulsifier in water is the continuous
phase wherein the monomer droplets and micelles (having the solubilised monomer
at their interior) are uniformly dispersed. If the monomer is slightly soluble in water,
then the aqueous emulsifier solution phase will also contain a part of the monomer
dissolved in it.
The difference between the suspension system and the emulsion system is
that, while both have monomer droplets, the emulsion system has, in addition
micelles in which the monomer is solubilised. If the quantity of the emulsifier added is
less than the CMC, the system becomes one of suspension polymerisation and only
when there is enough emulsifier to form the micelles, we can get an emulsion

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system. Emulsion systems generally utilise water-soluble initiators such as

persulfates or hydrogen peroxide. Redox initiators are also widely used.
In the emulsion polymerisation technique, we have a system where, as
already mentioned, the monomer is present as suspended droplets as well as
solubilised at the interior of the micelle. Whe n the initiator is water soluble and
monomer insoluble there is hardly any initiator in the monomer droplet and hence no
appreciable polymerisation occurs inside the monomer droplet. At the micelle,
however we have a very favourable condition for the polymerisation to occur. The
surface layer of the micelle formed by the polar ends of the emulsifier molecules is
highly hydrophilic and hence an appreciable concentration of the initiator is found at
this place. At the same time, the interior of the micelle is filled with the solubilised
monomer. Polymerisation therefore starts at the surface layer of the micelle and
proceeds inwards. As and when the monomer inside the micelle is consumed, more
monomer diffuses into the micelle from the monomer droplets present in the
aqueous phase. The chain growth continues till another radical species enters and
arrests the chain growth. With more and more polymer formation, the polymer chains
agglomerate into fine particles and get surrounded and then stabilised by the
emulsifier layer of the micelle. As the polymer particles concentration increases, it
absorbs the monomer and swells in size, which in turn enlarges the size of the
micelle. At a particular stage, however, the micelle bursts and loses its identity; all
the emulsifier molecules originally forming the micelle now form an absorption layer
around the polymer particles. Further supply of the monomer to the growing chain
inside the swollen polymer particle comes again from the monomer droplets.
Monomer droplets in this emulsion system, therefore act only as a reservoir where
from the monomer diffuses into micelles or polymer particles as the case may be.
At the end of the polymerisation, we have fine particles of the polymer,
stabilised by the emulsifier layer and dispersed uniformly in the aqueous phase. This
milky white dispersion is often called ‘latex’. The latex can either be used as such for
making adhesives, water-soluble emulsion paints etc or the polymer can be isolated
from the latex by destabilising the emulsion (using some electrolytes) by spray drying
or by freezing.
Emulsion polymerisation is the most widely used industrial technique and
monomers such as vinyl chloride, butadiene, chloroprene, vinyl acetate, acrylates
and methacrylates are polymerised by this technique. Heat transfer is very efficient
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and the viscosity build up of the polymerisation mass is quite low as compared to
that in the bulk and solution techniques. Since the polymerisation proceeds at the
micelles, where the surface/volume ratio is very high, the rate of polymerisation is
quite high. Also, since the number of radicals in a micelle is very much limited and
since there is a continuous supply of monomer to the growing chain, a very high
molecular weight product is achieved by this technique.

Classification of polymeric materials by performance

Plastic materials classifications divide polymers into four family groups based
on their application performance. The first is the “commodity plastics”. These
materials have large consumption volume, extensive application end uses, low
material cost and limited property and performance. The commodity plastics include
polystyrene, polyethylene, styrene acrylonitrile (SAN) copolymer, cellulose nitrate,
polybutene, bismaleimide, unsaturated polyeste r and polyvinyl chloride (PVC). The
second group is the “intermediate plastics”. These materials have higher mechanical,
thermal, chemical and electrical properties than the commodity plastics. The basic
polymer matrix properties remain constant; however, modifications can be made to
change specific properties of the compound.

Intermediate plastics include acrylic (polymethyl methacrylate (PMMA)),

polyolefin thermoplastic elastomer (TPO), modified polyphenylene oxide (PPO),
thermoplastic vulcanizate (TPV), melt processable rubber (MPR), high impact
polystyrene (HIPS), ionomers, polypropylene, glass fiber reinforced polypropylene,
ABS, styrenic block copolymer thermoplastic elastomers (TPEs) and ultra-high
molecular weight polyethylene.

The third group is the “engineering thermoplastics”. The level of mechanical

properties that qualify as engineering grade is somewhat arbitrary; a tensile strength
that is not lower than 7000 psi and a minimum modulus of elasticity of 3,50,000 psi
are resonable criteria. Engineering thermoplastic resins include polyacetal,
polyamide (nylon), polycarbonate, polybutadiene terephthalate (PBT), polyethylene
terephthalate (PET), block copolyester TPEs, polyamide TPEs, and liquid injection
molding silicone.

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The fourth group is the ‘high performance engineering materials”. These

materials have the highest resistance and retain a high percentage of their useful
mechanical properties at high temperatures, providing a longer service life of the
product.They also maintain properties at high electrical frequencies without
sacrificing their chemical resistance properties when exposed to corrosive elements.
These resins are also inherently flame retardant. The high performance engineering
resins include high temperature nylon (polyamide), liquid crystal polymers (LCPs),
polysulfone (PSU), fluoropolymers, polyetherimide (PEI), polyaryletherketone
(PAEK), polyphenylene sulfide (PPS), silicone polymers and polyimide. Competition
among resin producers to capture markets has created a resin supply of more than
26,000 resin grades in the USA alone. The result is that there is usually more than
one choice and often several choices available to meet the end-use performance
requirements.

POLYETHYLENE (PE)

Polyethylene is prepared from the polymerisation of ethylene monomer.

It is light weight, durable thermoplastic with variable crystalline structure. It is one of

the most widely produced plastics in the world. PE is used in applications ranging
from films, tubes, plastic parts, laminates and in several markets such as packaging,
automotive, electrical etc. It melts at 120 – 140oC.

Polyethylene is available in a range of flexibilities depending on the production

process. High density polyethylene (HDPE) is the most rigid of the three basic types
of polyethylene resins which also include LDPE and linear low density polyethylene
(LLDPE). HDPE can be processed by a wide variety of thermoplastic processing

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methods and is particularly useful where moisture resistance and low cost are
required. Polyethylene is limited by low end-use temperature characteristics. LDPE
is the second largest polyethylene in use by capacity in the USA. High molecular
weight LDPE film grade resins produce high-gloss, high-clarity films that exhibit good
toughness and heat sealing capability.

POLYVINYL CHLORIDE (PVC)

PVC is produced as a white powder containing coarse, porous particles.

Several additives are used during processing to give the polymers the desired
characteristics.

It is a high strength thermoplastic material widely used in pipes and medical devices.
It is an economical and versatile thermoplastic polymer widely used to produce door
and window profiles, pipes, wire and cable insulation etc.

All PVC compounds require heat stabilizers to allow processing without degrading
and discolouring the polymer. Plasticizers are added to increase the flexibility of the
compound. They can also improve the heat stability or improve the flame retardancy
of the compound. Fillers are used to reduce the cost, improve dimensional stability,
stiffness and impact strength. PVC is a recyclable commodity thermoplastic material
of large consumption by the building and construction industry. PVC is popular
because of its excellent impact, wear, chemical and UV resistance. PVC is used in a
large variety of end products such as flooring, garage doors, window frames and

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profiles, siding, tubing and connectors. These products are commonly available in
standard sizes and shapes, low cost and easy to work with (weld, repair and paint).

POLYTETRAFLUOROETHYLENE (PTFE)

These fluorocarbon resins are produced by the polymerization of

tetrafluoroethylene. PTFE is composed of long, straight chains of fluorinated carbons
(CF2 groups).

The chemistry of PTFE provides the unique characteristics of the polymer. The
helical backbone of carbon atoms symmetrically surrounded by fluorine atoms
provides the resin with its unique chemical, electrical and thermal properties. Like
most fluoropolymers, PTFE has outstanding electrical insulation properties. Its
dielectric constant (a quantity measuring the ability of a substance to store electrical
energy in an electric field) and loss factor (dissipation of heat) are low and uniform
across a wide temperature and frequency range. PTFE is flexible, strong and tough
at temperatures as low as -273oC. It has an opaque white colour and can be formed
into very thin and transparent films. PTFE polymers are available in granular, fine
powder and water base dispersion forms. PTFE has a high melt viscosity property
and the polymer never becomes liquid. At temperatures above 327 oC it becomes a
self-supporting gel. Because of these unusual melt characteristics, traditional
thermoplastic processing equipment canno t be used. However, one or more fillers
can be added to PTFE in some circumstances to prevent creep (tendency of a solid
material to move slowly or deform permanently under the influence of mechanical
stresses) or cold flow (viscous flow of a solid at ordinary temperatures) from
occurring when a load is applied to the soft material. Fillers are particularly desirable
when PTFE is used for parts in a dynamic operation where a high rate of wear may
occur. The fillers include fibreglass, carbon, graphite, bronze and molybdenum

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disulfide. There are copolymers of tetrafluoroethylene that can be processed by

traditional melt processing technologies and fluoropolymers that need special types
of processing techniques.

Structural properties and use of polycarbonate (PC)

PC is a thermoplastic material which offers a high performance tough,

amorphous and transparent thermoplastic polymer which has an organic functional
groups linked together by carbonate groups (-O-(C=O)-O-) and offers a unique
combination of properties. It is an engineering plastic.

Characteristics

• High impact strength, High dimensional stability,

• Good electrical properties,

• Light weight
• Protection from UV radiation

• Optical property with refractive index of 1.6.

• Good chemical resistance

Polypropylene

It is a tough and rigid crystalline thermoplastic produced from propylene. It is among

the cheapest plastics available today.

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Properties

• It is a tough, rigid, crystalline thermoplastic produced from propene monomer.

• It is a cheapest plastic available today.

• It has the lowest density among the commodity plastic.

• It is used in automotive industry, industrial applications, consumer goods,

furniture market.

NYLONS

Nylon is designated by the number of carbon atoms in its structure.

Nylon 6/6 or poly(hexamethylene adipamide) has six carbon atoms from the diamine
and six carbon atoms from the diacid components.

Nylon 6 has six carbon atoms from the -caprolactum (six carbon) monomer.

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Nylon is a semicrystalline, engineering thermoplastic material. It is a linear aliphatic

polyamide and is able to crystallize mostly due to the strong intermolecular hydrogen
bonds of the amide groups (-CO-NH-) sited regularly along the polymer chain and
the vander waals forces between the methylene chains.Nylon 6,6 has a m.pt of
264oC.It has good tensile strength and good abrasion resistance. It has good
toughness of upto 150oC. It offers resistance towards many solvents. It is soluble
only in formic acid, cresols and phenols. It also has high temperature stability and
self lubricating properties. It melts instead of burning. It is resistant to insects, fungi,
animals and many chemicals.

Uses

• Filaments for rope, carpet fibers, air bags, tyres, zip ties, conveyor belts.

• Ball bearing cages, electro-insulating elements, pipes, profiles etc.

• Textile fibers in dress, socks, shoes.

• Parachutes and swim wear

PHENOLIC RESINS

Phenol-formaldehyde thermosets were the first synthetic polymers. When a

stoichiometric deficiency of formaldehyde is used under acidic conditions, novolac
oligomers are produced. Novolacs must be cured with a second monomer that
reacts with the phenols.

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The predominant applications for phenol-formaldehyde thermosets are as adhesives

for plywood and as binders for similar wood products: hardboard, particle board and
molded wood products. For these applications, phenolic resins offer low cost and

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good compatibility with wood fiber. After cure, the thermoset has good resistance to
water. Phenolic resins are used as binders with glass and mineral ‘wool’ fibers to
make products suitable for thermal and acoustic insulation. In this application
phenolic resins are chosen because of their low cost, good thermal resistance (high
Tg), relatively good flame resistance and adhesion to fiber.

EPOXY RESINS

The most common applications for epoxies include adhesives, coatings (both
liquid and powder), composites and castings. Due to the formation of hydroxyl
groups during cure with most hardeners, epoxy thermosets have good adhesion to
metals and reinforcing fibers such as glass or carbon.

Epoxy thermosets are less brittle than most of the other thermosets . Common
adhesive applications are for automotive, aerospace, appliance and electronics.
Epoxy coatings are used as primer coats for automotive applied in water suspension,
as two-part liquid marine coatings and as powder coatings for automotive and
furniture.Epoxy formulations are used with reinforcing fibers to make composites for
windmill blades, printed circuit boards, pressure vessels, aerospace and automotive.
Epoxies are also used as casting resins for transformers and electric motors. For
large parts, care must be taken to avoid overheating during molding because the
heat release during cure can be substantial. Cost is the major factor that limits more
widespread use of epoxies.

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Polyaniline

The history of polyaniline can be traced to the studies of the dye aniline black.
The electrical conductivity of polyaniline was not reported until the mid-1980s by
MacDiarmid and coworkers. It was shown in these studies that polyaniline actually
has three distinct oxidation states and that all other apparent oxidation states are
really a mixture of two different oxidation states. The following figure represents the
simplest expression for the polyaniline structure expressed as a function of its
oxidation state consisting of alternating oxidised (1-y) and reduced (y) repeat units.

When the oxidation state of polyaniline is fully reduced (y=1) it is called

leucoemeraldine; when it is half oxidised (y=0.5), it is named emeraldine base and
when it is fully oxidised (y=0) it is termed pernigraniline. Emeraldine base is a weak
basic polymer as there are four nitrogen atoms in the polymer repeat unit, two
secondary amines and two tertiary imines. Polyaniline that is prepared in the
emeraldine oxidation state is the composition most often encountered and from a
technological point of view it is the most valued since it is environmentally stable and
has the most conductive state. Polyaniline has a conduction mechanism that is
unique among conducting polymers in that its most highly conducting doped form
can be reached by two different processes. Protonic acid doping of the emeraldine
base (y=0.5) or oxidative p-type doping of leucoemeraldine (y=1). Fully doped
emeraldine salt powders have conductivities in the range 1-10 S/cm whereas doped
films are more conductive (10-400 S/cm) at room temperature.

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Polypyrroles (PPy)

Polypyrrole is prepared by oxidation of pyrrole.

C4H2NH + 2n FeCl3  (C4H2 NH)n + 2nFeCl2 + 2nHCl

PPy can also be prepared by electrochemical polymerization, which is a particularly

good method because the growth rates and film thickness can be controlled. Early
preparation used sulphuric acid, but more recently the electrolyte has comprised
lithium chlorate in acetonitrile.Using electrodes made of platinum foils, gold or
conducting glass, PPy is obtained as a highly coloured (yellow) dense conducting
film. PPys have prompted considerable research, because they are one group of
conducting polymers that can be easily produced in the doped state (colour blue or
black). When a pyrrole monomer solution is electrolyzed in the presence of tetraethyl
ammonium and tetrafluroborate (Et4 N+ BF4-), a blue-black conducting polymer is
produced at the anode. The polymer can then be removed from the electrode and
has conductivities of up to 10 4 S m-1. One of the principal advantages of PPy over
other doped polymers is its excellent thermal stability in air. It is thermally stable up
to 250oC showing little degradation of its conducting properties below this
temperature. Above 250oC the rate of weight loss increases becoming very rapid

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over 600oC.Chemical analysis indicates that the pyrrole rings remain intact, with
each unit being connected by its  carbons.

Structure of PPy

+++++++++++++++++++++++++++++++++++++++++++++++++++

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